Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
  • C07C315/06—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C231/00—Preparation of carboxylic acid amides
  • C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
  • C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/26—Separation; Purification; Stabilisation; Use of additives

Definitions

• the present invention relates to the field of organic sulphides and more particularly that of alkyl sulphides or dialkyl sulphides, especially dimethyl sulphide (or dimethyl disulphide, or alternatively DMDS), and also that of the oxides thereof, and especially of dimethyl sulphoxide (or DMSO).
• organic sulphides have, in general, a strong, unpleasant, or even aggressive odour.
• DMDS has a strong and aggressive odour due in part to the presence of highly odorous impurities and in part to the garlicky and ethereal odour intrinsic to DMDS.
• the oxides of these organic sulphides, in particular DMSO have a less aggressive odour, but, depending on the concentrations of impurities, this odour can, however, be unpleasant, and an impairment for the end user.
• these other products may have odorous levels that are lower than that of DMDS and may, as a result, make their use preferred in certain cases.
• a particularly effective and economical method is the oxidation of methyl mercaptan by sulphur according to the invention:
• patent EP 0 446 109 In order to manufacture DMDS according to this process with high yields and a limited production of DMPS (dimethyl polysulphides with a rank greater than 2), patent EP 0 446 109, the content of which is incorporated herein by way of reference, describes a preparation process comprising two reaction regions interrupted by an intermediate degassing region and followed by a distillation region.
• U.S. Pat. No. 5,559,271 recommends adding thereto a certain amount of masking product such as, in particular, vanillin or ethyl vanillin.
• a certain amount of masking product such as, in particular, vanillin or ethyl vanillin.
• this patent is more particularly directed towards the treatment of heavy polysulphides, such as, for example, di-tert-nonyl pentasulphide. The application of this method to DMDS does not enable its unpleasant odour to be effectively masked.
• Patent EP 0 976 726 indicates that, in the specific case of DMDS having reduced contents of highly odorous volatile impurities such as methyl mercaptan and dimethyl sulphide, the most effective odour-masking agents are chosen from the esters of general formula R 1 CO 2 R 2 in which R 1 represents an optionally unsaturated, linear or branched hydrocarbon-based radical containing from 1 to 4 carbon atoms, and R 2 represents an optionally unsaturated, linear, branched or cyclic hydrocarbon-based radical containing from 2 to 8 carbon atoms.
• composition comprising:
• the odour-masking agent comprises:
• R a represents a linear or branched hydrocarbon-based chain containing from 1 to 6 carbon atoms, optionally comprising one or more unsaturation(s) in the form of one or more double bond(s)
• R b represents a cyclic hydrocarbon-based chain or else a linear or branched hydrocarbon-based chain optionally, but preferably, substituted with a cyclic structure, R b containing from 6 to 12 carbon atoms, optionally comprising one or more unsaturation(s) in the form of one or more double bond(s) and being optionally substituted with one or more hydroxyl groups; and
• the component a) used in the composition according to the present invention is an organic sulphide, optionally in oxide form, obtained according to any process known per se, or else commercially available, and preferably with a reduced content of volatile impurities.
• impurities are, for example, methyl mercaptan (MM) and dimethyl sulphide (DMS) in the case of DMDS; as regards DMSO, the impurities most commonly encountered are, for example, DMS, DMDS and/or BMTM (bis(methylthio)methane, also known as 2,4-dithiapentane).
• any method known to those skilled in the art for removing, or at the very least reducing, the abovementioned volatile impurities may be suitable; among said methods, mention may be made, in a nonlimiting manner, of distillation, evaporation under a stream of inert gas such as nitrogen, air and the like.
• the amounts of MM and of DMS present in the DMDS may advantageously be greatly reduced by distillation.
• This method has the advantage of jointly removing the MM and the DMS, whereas the usual methods for odour reduction are generally based on the elimination of the residual mercaptans by specific reaction of the mercaptan function with an eliminating agent such as a base or an alkene oxide in the presence of a base. These methods would have no effect on the DMS present in the DMDS.
• the residual contents of MM and DMS, after topping of the DMDS do not exceed 100 ppm and 50 ppm, respectively, by weight relative to the DMDS.
• the residual content of methyl mercaptan (MeSH) in the DMDS should not exceed 500 ppm by weight.
• the contents of impurities should advantageously be less than 100 ppm, preferably less than 50 ppm, more preferably less than 10 ppm, for each of the impurities taken separately.
• component a) of the composition according to the present invention corresponds to formula (1a):
• R and R′ which may be identical or different, are chosen from a linear or branched alkyl radical containing from 1 to 4 carbon atoms, and a linear or branched alkenyl radical containing from 1 to 4 carbon atoms; n is equal to 0; and x is an integer chosen from 1, 2, 3 or 4, preferably 2, 3 or 4.
• the component a) of formula (1a) is DMDS.
• component a) of the composition according to the present invention corresponds to formula (1b):
• R and R′ which may be identical or different, are chosen from a linear or branched alkyl radical containing from 1 to 4 carbon atoms, and a linear or branched alkenyl radical containing from 1 to 4 carbon atoms; n is equal to 0, 1 or 2; and x is equal to 0.
• the component a) of formula (1b) is DMSO.
• the masking of the odour of the organic sulphide or of the organic sulphides, and/or of the oxide form(s) thereof, corresponding to formula (1) described above, is obtained by addition, to said sulphides or oxides, of a composition defined in b) above.
• the present invention has the advantage of masking the unpleasant odour of at least one organic sulphide and/or of the oxide(s) thereof, without chemically modifying the nature thereof.
• the present invention proposes a composition comprising a) a predominant amount of at least one organic sulphide of formula (1) defined above, to which a minor amount of a composition b) masking the unpleasant odour of the component a) is added.
• composition with masked odour according to the present invention may be prepared according to any process known per se by simply combining at least one component a) with at least one odour-masking composition b). It is, for example, possible to add at least one composition b) to at least one component a), or vice versa, optionally with stirring and/or optionally with heating. More generally, any known mixing and/or heating method may be used.
• the preparation of the composition according to the invention may, for example, be carried out under atmospheric pressure, at a temperature of between 0° C. and 100° C., preferably between ambient temperature and approximately 80° C.
• the preparation may also be carried out under pressure or at a reduced pressure, at temperatures within the ranges indicated above.
• the period of time required for the preparation of the composition with masked odour according to the invention varies according to the nature and the amount of the component(s) a) and of the composition(s) b) but also as a function of the temperature and of the pressure selected. As a general rule, this period corresponds to the period of time necessary for obtaining a homogeneous mixture and producing the desired effect of masking the odour of the component(s) a); it is generally between a few seconds and a few minutes, or even one or more hours.
• the preparation process mentioned above can be prepared batchwise (batch process) or else continuously.
• composition b) is mixed, according to any method known to those skilled in the art, with the component a) in an amount ranging from a few ppm, for example 10 ppm, to 2%, preferably from 10 ppm to 1% by weight relative to the total weight of the composition.
• the amount of masking agent (composition b)) can vary to a large extent within the range indicated above, depending on the desired effect, the strength of the odour to be masked, the respective residual contents of the various impurities that may be present in the component(s) a) defined above, and the like.
• Amounts of masking agent of less than a few ppm may be too small to obtain the desired effect. Amounts of masking agent greater than 2% may have harmful effects depending on the applications envisaged for the organic sulphides and/or oxides.
• the content of odour-masking agent(s) b) is between 0.001% and 0.5% by weight relative to the total weight of the composition, and more particularly between approximately 0.1% and 0.5% by weight, advantageously equal to approximately 0.3%, in particular when the organic sulphide of which it is desired to mask the odour is DMDS.
• the maximum content of odour-masking agent(s) is advantageously between 0.001% and 0.2% by weight relative to the total weight of the composition, preferably between 100 ppm and 1000 ppm, for example approximately 500 ppm by weight.
• the composition according to the present invention comprises at least one composition of odour-masking agent b), said agent comprising from 1% to 40%, preferably from 2% to 35%, more preferably from 5% to 30% by weight, relative to the total weight of the composition b), of at least one monoester mentioned in b1).
• C 2 -C 20 acid esters such as ethyl, propyl, butyl, pentyl, 2-methylbutyl, isoamyl, hexyl, benzyl, phenylethyl, menthyl or carvyl acetates, propionates, butyrates, methylbutyrates, pentanoates, hexanoates, heptanoates, caproates, oleates, linoleates and linolenates, and the like, and also mixtures thereof.
• saturated or unsaturated C 2 -C 20 acid esters such as ethyl, propyl, butyl, pentyl, 2-methylbutyl, isoamyl, hexyl, benzyl, phenylethyl, menthyl or carvyl acetates, propionates, butyrates, methylbutyrates, pentanoates, hex
• Isoamyl acetate, hexyl acetate, 2-methylbutyl butyrate, isoamyl butyrate, benzyl acetate, phenylethyl acetate and mixtures of these compounds are more particularly preferred.
• the odour-masking agent composition b) also comprises at least one di- and/or triester b2), in an amount of between 10% and 70% by weight, preferably between 15% and 65% by weight, more preferably between 20% and 60% by weight, such as, in a nonlimiting manner, at least one di- and/or triester chosen from ortho-phthalates, such as diethyl ortho-phthalate; citrates, such as triethyl citrate; and malonates, such as diethyl malonate.
• ortho-phthalates such as diethyl ortho-phthalate
• citrates such as triethyl citrate
• malonates such as diethyl malonate.
• the odour-masking agent b) also comprises from 1% to 30%, preferably from 5% to 25% by weight relative to the total weight of the composition, of at least one alcohol b3), advantageously at least one monoalcohol containing from 1 to 30 carbon atoms, preferably from 6 to 20 carbon atoms, more preferably from 8 to 11 carbon atoms, said carbon atoms forming a linear or branched chain optionally comprising one or more unsaturation(s) in the form of one or more double bond(s), and optionally comprising a 5- or 6-membered cyclic structure which is saturated or completely or partially unsaturated.
• the alcohols defined above are preferably monoalcohols, the hydroxyl function preferably being borne by an sp 2 carbon atom. It should be understood that the hydroxyl function may also be borne by a carbon atom included in a cyclic structure as defined above.
• the alcohols used in the odour-masking agent and as defined above are advantageously, and by way of nonlimiting examples, chosen from menthol, neomenthol, phenylethyl alcohol, benzyl alcohol, citronellol, dihydromyrcenol, dihydroterpineol, dimetol, ethyllinalol, geraniol, linalol, tetrahydrolinalol, tetrahydromyrcenol, nerol, and the like, and also mixtures of two or more thereof.
• the ketone or the ketones indicated in b4) above are chosen, by way of nonlimiting examples, and preferably, from damascones, damascenones, ionones, irisones, methylionones, frambinone (CAS No. 5471-51-2), and the like, and also mixtures thereof.
• the amount of ketone(s) is advantageously between 0.5% and 20%, preferably between 1% and 10% by weight relative to the total weight of the composition.
• the odour-masking agent may optionally also comprise up to 20%, preferably from 1% to 10% by weight relative to the total weight of the composition, of at least one terpene.
• terpenes As examples of terpenes, indicated in b5), which can be used, mention may be made, in a nonlimiting manner, of terpinenes, myrcene, limonene, terpinolene, pinenes, sabinene, camphene, and the like, mixtures of two or more thereof, and also essences based on terpenes, in particular those comprising these ingredients.
• the odour-masking agent that can be used in the context of the present invention may comprise, in minor amounts, other agents (fragrances) customarily used in the perfumery field, and in particular one or more compounds bearing cyclic ketone and/or aldehyde function(s), among which mention may be made, in a nonlimiting manner, of geranial, neral, citronellal, menthone, isomenthone, 1,8-cineole, ascaridole, flavonone, and mixtures thereof.
• composition b) intended to mask the odour of the organic sulphides, and as described above, may, where appropriate, or if necessary, also comprise one or more additives commonly used in the field.
• additives may, for example, be chosen, in a nonlimiting manner, from solvents, pigments, dyes, preservatives, biocides and the like.
• the solvents most particularly preferred examples are alcohols, ethers, esters and glycols.
• the solvent is chosen from diethyl phthalate, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycols, polypropylene glycols, and mixtures thereof, and even more advantageously from diethyl phthalate, dipropylene glycol, and mixtures thereof.
• a monoester, diester or triester present in the odour-masking agent composition b), as component b1) and/or b2), may also have the functions of the solvents defined above.
• a typical odour-masking agent composition suitable for organic sulphides and oxide forms thereof, according to the present invention, comprises by weight:
• composition Ci is most particularly suitable for masking the odour, or for improving the odour, of DMDS.
• This same composition Ci may also be advantageously used for masking or improving the odour of DMSO.
• composition Ci A representative but nonlimiting example of such a composition Ci is reproduced below, in which each of the components comprises one, several, or even all the compounds listed:
• compositions are given by way of examples and are in no way restrictive with regard to the potential diversity of compositions permitted by the present invention defined by means of the attached claims.
• PE polyethylene
• a crystallizing dish containing two sheets of absorbent paper (chromatography paper) is placed in each of the drums. 1 ml of test composition is poured onto each sheet. The drums are stored closed for 24 hours at ambient temperature. The evaluation is subsequently carried out blind.
• the panelists of which there are ten, come in turn to test a few products per session (a maximum of three products per session). They begin by smelling the drum containing the reference DMDS for this study, and then one of the test compositions.
• the panelists assign, according to their preference, a score to each of the test compositions, relative to the reference which arbitrarily received the score 5.
• the scores given by the panelists range from 1 (the most pleasant product) to 10 (the most unpleasant product).
• the DMDS without odour-masking agent, is an industrial DMDS produced by Arkema, has a purity of greater than 99.7% and contains less than 100 ppm of methyl mercaptan and less than 50 ppm of dimethyl sulphide.
• DMDS Added to this DMDS are 3000 ppm of a fragrancing composition having the following composition: 25% isoamyl acetate, 50% diethyl ortho-phthalate, 15% 2-methylbutyl butyrate and 10% benzyl acetate, as described in patent EP 0 976 726.
• This sample is the reference sample for the olfactory test and is called: A1.
• 3000 ppm of the fragrancing composition Ci according to the invention and defined above are added to the same industrial DMDS produced by Arkema without odour-masking agent. This sample is called: A2.
• the SSD test is a statistical test for comparison of means and makes it possible to determine whether or not the means of two samples are significantly different, from a statistical point of view.
• the statistical condition used is fixed at 95%. If the means are not significantly different, the two samples are classified in the same group. If the means are significantly different, the two samples constitute two separate groups (A and B in the examples that illustrate the invention).
• the reference DMSO is an industrial DMSO with a purity equal to 99.97%, produced by Arkema, and then supplemented with 50 ppm of dimethyl sulphide (DMS). This sample is called B1.

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